Oxalkylation products produced from epoxides and amines and their use in pigment preparations

ABSTRACT

The invention relates to addition compounds of formula (1) in which: n is a number from 1 to 10; Z represents a group —CH 2 —CH 2 —, —CH 2 —CH(CH 3 )—, —CH(CH 3 )CH 2 — or a combination thereof; s is number from  1  to 200; B represents hydrogen, —CO—CH═CH—COOM, COCH(SO 3 M)CH 2 COOM, —CO—CH 2 —CH(SO 3 M)-COOM, —SO 3 M, —SO 2 M and/or —PO 3 MM, whereby M is preferably a cation selected from the group Li + , Na + , K + , NH 4   + , HO—CH 2 —CH 2 —NH 3   + , (HO—CH 2 —CH 2 —) 3 NH + , and; Y is a radical of an amine of formula (4). The inventive addition compounds are used as dispersing agents of solids, for example, pigments, particularly in aqueous media.

[0001] The present invention lies in the field of interface-active,surfactant compositions and relates to oxalkylated addition compoundsobtained by reacting polyepoxides with amines. The invention furtherrelates to the preparation of the addition compounds and to their use asdispersants for solids, particularly pigments.

[0002] In the preparation of dispersions of solids it is common to usesurface active substances which are intended to reduce the mechanicaleffort involved in dispersing the solids into liquid media. Whenpreparing preparations and dispersions of colorants, such as dispersedyes, or organic and inorganic pigments, for applications in aqueous ororganic media a large number of nonionic, anionic, and cationicsurfactants is employed for this purpose. During the incorporation ofpigments and their preparations into coatings systems, printing inks,and plastics further difficulties occasionally arise, since theflocculation-stable fine division of numerous pigments in the respectiveapplication medium can be achieved only to a very inadequate extent andwith a great deal of dispersing effort. The performance properties,consequently, are very often inadequate. Thus even during the dispersingoperation or else only thereafter it is possible for flocculationphenomena and sedimentation to occur, leading in the colored materialsto unwanted changes in the viscosity of the application medium, tochanges in shade and losses of color strength, hiding power, gloss,homogeneity, and brightness, and also to poorly reproducible shades andto a high propensity to run in the case of paints.

[0003] U.S. Pat. No. 3,853,770 describes adducts of polyepoxides andsecondary amines as softeners for textile materials.

[0004] These products however, are incapable of providing a decisiveimprovement in the fluidity or flocculation stability of aqueous pigmentdispersions without at the same time adversely affecting otherparameters such as color strength, gloss, shade and cleanness of color,for example.

[0005] EP-A-0 071 861 describes addition compounds which are obtained byreacting diepoxides derived from bisphenol A with phenols and aresubsequently also oxalkylated. The dispersing of pigments is describedas a field of application of these compounds, most of which are solublein water.

[0006] EP-A-0 044 025 and DE-A-29 13 176 describe compounds which arelikewise obtainable by reacting diepoxides derived from bisphenol A andether amines, and which are subsequently also oxalkylated. Thesecompounds, which are likewise water-soluble, are also described asdispersants of pigments. The products described in these publications,however, are often incapable of ensuring the fluidity and theflocculation stability in pigment dispersions without adverselyaffecting other parameters, such as the color strength, for example.

[0007] U.S. Pat. No. 5,070,159 describes adducts prepared frompolyepoxides and a mixture of aliphatic, aromatic and/or heterocyclicamines. The polyepoxides are synthesized on the basis of 2,3-epoxypropylnovolaks having 3 to 11 nuclei. The addition compounds described,however, are not oxalkylated and are described as dispersants for solidsexclusively in organic media.

[0008] The present invention was based on the object of providinginterface-active auxiliaries for dispersions of solids that are suitablefor the preparation of highly fluid, flocculation-resistant, andstorage-stable dispersions of solids, preferably dispersions ofcolorants, for exterior and interior coating, are substantially freefrom the disadvantages specified above, and are not based on bisphenolA.

[0009] It has been found that below-defined oxalkylation productsprepared from epoxides and amines surprisingly achieve these objects.

[0010] The present invention provides addition compounds of the formula(1),

[0011] in which

[0012] n is a number from 1 to 10, for example, 1, 2, 3, 4, 5 or 6;

[0013] R¹, R² are identical or different and are each a hydrogen atom ora saturated or unsaturated aliphatic radical having 1 to 4 carbon atoms;

[0014] R³, R⁴ are identical or different and are each a hydrogen atom oralkyl having 1 to 3 carbon atoms, and the bridge member

[0015] is in each case positioned ortho or meta in relation to thephenolic oxygen atom;

[0016] Z is a group —CH₂—CH₂—, —CH₂—CH(CH₃)—, —CH(CH₃)—CH₂— or acombination thereof,

[0017] s is a number between 1 and 200,

[0018] B is hydrogen, —CO—CH═CH—COOM, —COCH(SO₃M)CH₂COOM,—CO—CH₂—CH(SO₃M)-COOM, —SO₃M,

[0019] —SO₂M and/or —PO₃MM, M being a cation, preferably from the groupLi⁺, Na⁺, K⁺, NH₄ ⁺, HO—CH₂—CH₂—NH₃ ⁺, (HO—CH₂—CH₂—)₂NH₂ ⁺ or(HO—CH₂—CH₂—)₃NH⁺ and

[0020] Y is a radical of an amine of formula (4)

[0021] in which

[0022] R⁵ is a saturated or singly or multiply unsaturated aliphaticradical having 6 to 30 carbon atoms,

[0023] A is phenylene or naphthylene,

[0024] p is zero or 1,

[0025] R⁶, R⁷ are each hydrogen or a methyl radical, but are notsimultaneously a methyl radical, and

[0026] q is a number from 0 to 40;

[0027] and/or Y is a radical of an amine of the formula (S)

[0028] in which

[0029] r is a number from 0 to 2,

[0030] R⁸ is a saturated or singly or multiply unsaturated aliphaticradical having 8 to 24 carbon atoms, and

[0031] R⁹ is an alkylene group having 2 to 6 carbon atoms,

[0032] and/or Y is a radical of the amines of the formulae (6), (7), (8)and/or (9)

[0033] in which

[0034] t is 0 or 1,

[0035] R¹⁰ is an alkylene group having 1 to 10 carbon atoms,

[0036] R¹¹ is an alkylene group having 2 to 6 carbon atoms,

[0037] R¹² is a hydrogen atom or an alkyl group having 1 to 4 carbonatoms,

[0038] R¹³ is a saturated or a singly or multiply unsaturated,mononuclear or polynuclear heterocyclic or carbocyclic ring systemhaving 3 to 18 carbon atoms which if desired also contains in the ring1, 2 or 3 further heteroatoms from the group N, S and O, it beingpossible for the ring system to be substituted by one or more, e.g., 1,2 or 3, of the radicals R¹⁷, halogen atoms such as —F, —Cl and —Br,—OR¹⁷, —NR¹⁷R¹⁸, —COOR¹⁷, —CONR¹⁷R¹⁸, —NR¹⁷—COR¹⁸, —NO₂, —CN or CF₃, R¹⁷and R¹⁸ independently of one another being hydrogen or an alkyl radicalhaving 1 to 10 carbon atoms, in particular hydrogen or an alkyl grouphaving 1 to 4 carbon atoms,

[0039] R¹⁴, R¹⁵ are identical or different and are each a saturated orsingly or multiply unsaturated aliphatic radical having 1 to 24 carbonatoms; and

[0040] R¹⁶ together with the nitrogen atom of the formula (9) forms a 5-to 7-membered heterocyclic ring system which if desired also contains inthe ring 1, 2 or 3 further heteroatoms from the group N, S and O, itbeing possible for the ring system to be substituted by one or more ofthe radicals R¹⁷, halogen atoms such as —F, —Cl, and —Br, —OR¹⁷,—NR¹⁷R¹⁸, —COOR¹⁷, —CONR¹⁷R¹⁸, —NR¹⁷—COR¹⁸, —NO₂, —CN or CF₃.

[0041] The invention also provides mixtures of addition compounds of theformula (1), so that the number n may also adopt fractional values, suchas from 1.1 to 10, for example, preferably from 1.2 to 6.

[0042] R¹ and R² are preferably hydrogen or methyl.

[0043] R³ and R⁴ are preferably hydrogen or methyl.

[0044] Preferably s is a number from 5 to 100, in particular from 10 to40.

[0045] M is preferably hydrogen, an alkali metal or ammonium ion, whichcan be alkyl-substituted.

[0046] R⁵ is preferably a C₆-C₁₈-alkyl or C₆-C₁₈-alkenyl.

[0047] Preferably q is a number from 2 to 25, in particular from 4 to12.

[0048] Preferably r is the number 1 or 2.

[0049] R⁸ is preferably C₁₂-C₂₀-alkyl or C₁₂-C₂₀-alkenyl.

[0050] R⁹ is preferably propylene or butylene.

[0051] Preferably t is 1.

[0052] R¹⁰ is preferably C₁-C₆-alkylene.

[0053] R¹¹ is preferably ethylene or propylene.

[0054] R¹² is preferably hydrogen or methyl.

[0055] R¹³ is preferably phenyl, naphthyl, pyrazolyl, triazolyl,piperidinyl, oxazolidinyl, imidazolyl, pyrrolyl, pyrrolidinyl,carbazolyl, benzothiazolyl, benzimidazolyl, dihydropyrrolyl,dihydropyrazolyl and oxazolidonyl.

[0056] R¹⁴ and R¹⁵ are preferably C₁-C₁₂-alkyl or C₂-C₁₂-alkenyl.

[0057] The compound of the formula (9) is preferably pyrazole, triazole,piperidine, oxazolidine, imidazole, pyrrole, pyrrolidine, carbazole,dihydropyrrole, dihydropyrazole, oxazolidone, morpholine,dihydropyridine or azepine.

[0058] The invention also provides a process for preparing the additioncompounds of the formula (1) by reacting an epoxy compound of theformula (2)

[0059] in which X has the definition 2,3-epoxypropyl,

[0060] with one or more amines of the formulae (4) to (9), oxalkylatingthe product, and subjecting the resulting oxalkylate, where appropriate,to monoesterification with maleic anhydride and, where appropriate, tosulfation.

[0061] The invention further provides the reaction product obtainable bythe process described above.

[0062] Suitable epoxides of the formula (2) include commerciallycustomary polyfunctional epoxides based on novolaks. Novolaks can becondensed by conventional processes, e.g., by condensing phenols and/oralkylphenols with alkanals in the presence of acidic catalysts.

[0063] The

[0064] group is in the o- or m-position in relation to the —O—X group.

[0065] For the synthesis of the epoxides the phenolic hydroxyl groupsare reacted by conventional processes, as described for example in U.S.Pat. No. 2,505,486, for example, with epichlorohydrin to give theglycidyl ether.

[0066] Of particular interest are polyepoxides of the formula (2) inwhich R¹ and R² independently of one another are each a hydrogen atom,methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, sec-butyl or tert-butyl. Theformula (2) is to be regarded as an idealized formula and therefore alsodescribes all commercially customary polyepoxides in which as a resultof side reactions during the introduction of the epoxy group onto thephenolic hydroxyl group not all the hydroxyl groups are etherified andconverted to the 2,3-epoxypropyl radical. Starting product for theprocess of the invention are therefore also polyepoxides in which up to30% of all X in the formula (2) describe other radicals deriving fromthe synthesis e.g. 2,3-dihydroxy-prop-1-yl and/or3-chloro-2-hydroxy-prop-1-yl radicals. The skilled worker is aware,moreover, that the preparation of novolaks by conventional processes,e.g., by condensing phenols and/or alkylphenols with alkanals in thepresence of acidic catalysts, may often give rise to mixtures ofdifferent condensates. Since for reasons of cost such mixtures aregenerally not separated into pure species, the index n may also adoptvalues which deviate from the integral numbers.

[0067] One example of commercially customary polyepoxides of the formula(2) are, for example, ®ARALDITES.

[0068] The secondary ether amines of the formula (4) are obtainable forexample in accordance with the process described in DE-A-2 555 895. Inthat process oxalkylates of the formula (10)

[0069] are reacted in liquid phase with ammonia and hydrogen in thepresence of (de)hydrogenation catalysts, examples being nickel catalystsand cobalt catalysts.

[0070] Suitable radicals R⁵ of the secondary ether amines of the formula(4) include in particular the alkyl radicals of fatty alcohols obtainedfrom natural fats and oils and also of alcohols from the oxo process. Ofthe amines as described for the formulae (4), (5), (6), (7), (8), and(9) mention may be made of the following:

[0071] octylamine, decylamine, dodecylamine, tetradecylamine,hexadecylamine, octadecylamine, coconut fatty amine, laurylamine,oleylamine, rape seed oil fatty amine, stearylamine, tallow fatty amine,dicocoalkylpentaoxoethylamine, didecylamine, diisotridecylamine,distearylamine, ditallow fatty amine, dicoconut amine, tallow fattypropylene diamine, oleylpropylenediamine, laurylpropylenediamine,N,N-bis(aminopropyl)-tallow fatty amine, 1-(3-aminopropyl)imidazole, andfurfuryl amine.

[0072] In the reaction of the amines with the polyepoxide of the formula(2) it is preferred to react from 50 to 100%, in particular from 70 to100%, of the 2,3-epoxypropyl radicals with an amine of the formula (4)or with mixtures of two or more amines of the formula (4) and alsopreferably from 0 to 50%, in particular from 0 to 30%, with amines ofthe formula (5), (6), (7), (8) and/or (9).

[0073] The epoxide is preferably reacted in one reaction step with acorresponding amine or the amine mixture. This reaction can be conductedin the presence or absence of solvents which are inert or at least ofnegligible reactivity under the reaction conditions. Examples that maybe mentioned include hydrocarbons, especially aromatic hydrocarbons suchas toluene, for example, or ethylene glycol ethers such as ethyleneglycol monomethyl ether, for example. The reaction can be conducted attemperatures from 0 to 200° C., preferably from 40 to 160° C. It isappropriate to conduct the reaction in the absence of oxygen.Particularly suitable catalysts for the epoxide ring opening includeacidic catalysts such as aluminum chloride, for example, or phenols.

[0074] Subsequent oxalkylation of the amine-opened glycidyl ethers onthe hydroxyl group takes place in accordance with known methods,preferably with alkali metal hydroxides or alkali metal alkoxides ascatalyst at 100 to 200° C., preferably at from 140 to 180° C. The amountof ethylene oxide and/or propylene oxide is made such that the adductscan be stably emulsified or fully dissolved in water. For each hydroxygroup of the 1,2-amino alcohol group it is preferred to add on from 1 to200, preferably from 10 to 40, mol of ethylene oxide and/or propyleneoxide. An alternative option is first to insert a polyoxypropylene chainusing propylene oxide and then to insert a polyoxyethylene chain usingethylene oxide. The amount of alkylene oxide added on also depends onthe intended end use and the associated target degree of hydrophilicity.The alkali metal hydroxide is suitably potassium hydroxide and/or sodiumhydroxide, the alkali metal alkoxide sodium methoxide or ethoxide. Theconcentration of the catalyst ought preferably to be from 0.05 to 2% byweight, based on the amine-glycidyl ether adduct, at the beginning ofthe oxalkylation. The oxalkylation can be conducted withoutsuperatmospheric pressure or in pressure vessels using propylene oxideor, preferably ethylene oxide or mixtures of both, it being possible tosupply the alkylene oxide in gas or liquid form. The operating pressurewhen carrying out the reaction in pressure vessels is from 1 to 10 bar,preferably from 2 to 6 bar. The compounds or mixtures of compoundsobtained can be used either directly or in an aqueous and/or organicsolution, depending on the intended end use.

[0075] Where the intended end use of the dispersant dictates that theterminal hydroxyl groups are to be reacted further, they can beconverted fully or partly into the corresponding maleic monoesters witheither corresponding stoichiometric or substoichiometric amounts (basedon the terminal hydroxyl groups) of maleic anhydride or other reactivemaleic acid derivatives. The monoesterification is accomplished bymixing and stirring, for example, maleic anhydride with the oxalkylatedamine-glycidyl ether adduct at 10 to 110° C., preferably at from 40 to80° C., optionally in the presence of alkali metal hydroxides, whoseconcentration should be from 0.1 to 2.0% by weight, based on the overallmixture. Since maleic anhydride has a tendency to sublime it may beadvantageous from a process engineering standpoint to operate inpressure vessels under a superatmospheric pressure of about 0.2 to 1.0bar of inert gas and also to ensure vigorous commixing.

[0076] Conversion of the maleic monoesters to the correspondingsulfosuccinic monoesters is accomplished by adding aqueous sulfitesolution or hydrogensulfite solution. The amount of the solution can bemade such that either all or only some of the maleic monoester groupsare converted to sulfosuccinic monoester groups. For each maleicmonoester group to be reacted from 1.0 to 2.0 equivalents, preferablyfrom 1.05 to 1.15 equivalents, of alkali metal or alkaline earth metalsulfite, hydrogen sulfite or disulfite are used. Where aqueous solutionsof sulfites are used in this reaction the corresponding neutral salts ofthe sulfosuccinic monoesters are formed. Where aqueous solutions ofhydrogen sulfites are used, acidic monoester salts are formed. Theamount of water added can amount to from 30 to 90% by weight, based onthe overall solution or mixture. It is dependent in particular on thesolubility of the sulfosuccinic monoesters and on the viscosity of thesolution.

[0077] The compounds of the invention are suitable for dispersingsolids, particularly in aqueous liquids. Mention may be made ofdispersions comprising solids, for example, finely divided ores,minerals, sparingly soluble or insoluble salts, particulate waxes orpolymers, crop protection and pest control agents, optical brighteners,UV absorbers or light stabilizers, especially dyes and organic orinorganic pigments.

[0078] The present invention further provides pigment preparationscontaining

[0079] a) from 1 to 80% by weight, preferably from 5 to 60% by weight,in particular from 10 to 50% by weight, of one or more pigments;

[0080] b) from 1 to 50% by weight, preferably from 5 to 40% by weight,in particular from 8 to 30% by weight, of at least one compound of theformula (1) or at least one of the oxalkylation products of epoxides ofthe formula (2) and amines of the formulae (4) to (9) prepared by theprocess described above;

[0081] c) from 0 to 50% by weight, in particular from 0 to 30% byweight, of further additives; and

[0082] d) from 10 to 80% by weight of water,

[0083] based in each case on the overall weight (100% by weight) of thepigment preparation.

[0084] The pigments that may be present in the preparations of theinvention are not subject to any restriction. They may be organic orinorganic in nature. Examples of organic pigments for the purposes ofthe invention are monoazo pigments, disazo pigments, laked azo pigments,triphenylmethane pigments, thioindigo pigments, thiazineindigo pigments,perylene pigments, perinone pigments, anthanthrone pigments,diketopyrrolopyrrole pigments, dioxazine pigments, quinacridonepigments, phthalocyanine pigments, isoindolinone pigments, isoindolinepigments, benzimidazolone pigments, naphthol pigments and quinophthalonepigments. Particular mention ought also to be made of acidic to alkalinecarbon blacks from the group of the furnace blacks or gas blacks.

[0085] Examples of suitable inorganic pigments include titanium dioxide,zinc sulfides, iron oxides, chromium oxides, ultramarine, nickel orchromium antimony titanium oxides, cobalt oxides, and bismuth vanadates.

[0086] Examples of further customary additives are anionic, cationic ornonionic surfactants, additives for adjusting the rheology, pigmentderivatives which act as dispersants, e.g., N—(C₁₀-C₃₀)-alkyl- orN—(C₁₀-C₃₀)-alkenyl-phthalimides, the urea compounds specified in EP-A-0542 052, foam suppressants, preservatives, framework substances whichcan be used in emulsifying and dispersing formulations, dryoutpreventatives, such as glycols, for example, such as propane-1,2-diol,monoethylene glycol or diethylene glycol, higher molecular masspolyether polyols possessing a molecular weight, determined as thenumerical average, of from 250 to 10000, in particular from 250 to 2000,having a boiling point under atmospheric pressure of more than 150° C.Suitable polyether polyols include homo-, co- or block-co-polyetherpolyols, which can be prepared by reacting ethylene oxide and/orpropylene oxide with water or with low molecular mass alcohols oramines.

[0087] Suitable surfactants include all known anionic, cationic, andnonionic interface-active compounds. Surfactants which have been foundto be particularly appropriate are those which possess one or more thanone medium- or long-chain hydrocarbon chain. Of the multiplicity of thecompounds only a selection will be listed at this point, though withoutrestricting the applicability of the compounds of the invention to theseexamples. Examples are alkyl sulfates, alkyl sulfonates, alkylphosphates, alkylbenzene sulfonates, such as lauryl sulfate, stearylsulfate, dodecyl sulfonates, octadecyl sulfates, dodecyl sulfonates,condensation products of fatty acid and taurine or hydroxyethanesulfonic acid, alkoxylation products of alkyl phenols, castor oil rosinesters, fatty alcohols, fatty amines, fatty acids, and fatty acidamides, reaction products of nonylphenol and shorter-chain, substitutedalkyl phenols and also their polymeric derivatives, e.g., formaldehydecondensation products, and also polymeric compounds such aspolyacrylates, for example.

[0088] Aqueous dispersions prepared on this basis are outstandinglysuitable for pigmenting both hydrophilic and hydrophobic systems and arenotable for a very low drying or dryup tendency.

[0089] One feature deserving a particular emphasis is the markedlyimproved redispersibility of fractions of preparation that have dried ordried out.

[0090] The present invention additionally provides a process forproducing the pigment preparations of the invention by adding thecompound(s) of the formula (1) and, where appropriate, the furtheradditives during the pigment synthesis or during one of the customaryprocessing steps such as grinding, dispersing or finishing or else notuntil the pigment is incorporated into the application medium. Thecompound of the formula (1) can be added here in pure or dissolved formto the pigment, which is in the form of a solid or a dispersion in wateror an organic solvent. Dispersing and grinding operations take place inaccordance with the grain hardness of the pigment used in a known way,for example, in sawtooth stirrers (dissolvers), rotor-stator mills,turbulent high-speed mixers, ballmills, sandmills or beadmills, inkneading units or on roll mills.

[0091] The liquid to paste like pigment preparations produced in thisway are available for any purpose for which colorant dispersions cannormally be employed and for which stringent requirements are imposed onflocculation stability and/or storage stability, changes in theviscosity of the application medium, changes in shade, color strength,hiding power, gloss, homogeneity, and brilliance.

[0092] Accordingly they are suitable, for example, for coloring naturaland synthetic materials. They are of particular value for thepigmentation of paints, including emulsion paints, dispersion varnishes,for printing inks, examples being textile printing, flexographicprinting or gravure printing inks, for wallpaper inks, forwater-thinnable coating materials, for wood preservation systems, forplasters, for wood stains, for paper pulps, for colored pencil leads,for fibertip pens, water colors, pastes for ballpoint pens, chalks,detergents, including cleaning products, shoe polishes, coloring oflatex products, abrasives, and for coloring plastics and high molecularmass materials.

[0093] The pigment dispersions of the invention are also suitable foruse as colorants in electrophotographic toners and developers, such asone- or two-component powder components, (also called one- ortwo-component developers), magnetic toners, liquid toners,polymerization toners, and further specialty toners (L. B. Schein,“Electrophotography and Development Physics”; Springer Series inElectrophysics 14, Springer Verlag, 2^(nd) edition, 1992). The pigmentdispersions of the invention are additionally suitable for use ascolorants in ink-jet inks, based on both aqueous and nonaqueous systems,and also in those inks which operate in accordance with the hot-meltprocess or are based on microemulsions.

[0094] The pigment dispersions of the invention can be mixed in anyproportion with water and feature outstanding flocculation stability andstorage stability in many aqueous emulsion paints, in comparison toconventional pigment dispersions. Where the pigment dispersions areprepared using additives which are compatible with hydrophobic paintbinder systems, it is then possible to produce dispersions which arealso stable to flocculation in hydrophobic media. Qualities deserving ofparticular emphasis are the good rheological properties and also theexcellent dispersibility in different application media. The dispersantsof the invention thus make it possible, alone or in combination withsuitable other auxiliaries, to achieve the full color strength andbrightness of the pigments in the dispersing operation and stabilizethose qualities durably in the application medium. Light-colored andbright shades are unimpaired by the slight intrinsic coloring of thedispersants of the invention.

[0095] The examples which follow serve to illustrate the invention;percentages are by weight, parts denote weight fractions. Viscositieswere measured at 23° C. using a cone and plate viscometer, and are basedon a shear rate of D=60 sec⁻¹. Room temperature denotes a temperature ofapproximately 25° C.

PREPARATION EXAMPLE 1

[0096] A stirred vessel was charged with 457.5 parts of an amine of theformula (4) with R⁶, R⁷=hydrogen, R⁵=alkyl radical of coconut fattyalcohol, p=0, and q=5, and with 0.26 part of phenol under an inert gasatmosphere. This mixture was heated to an internal temperature of 100°C. and, at this temperature, 129.6 parts of a finely powderedpolyepoxide of the idealized structure in formula (2) with R¹=2-methyl,R², R³, R⁴=hydrogen, n=5, epoxy equivalent weight 225 [g/eq] (®AralditeECN 1273), were added over the course of 5 minutes. The mixture washeated over the course of 45 minutes to an internal temperature of 150°C. and the reaction mixture was stirred at this temperature for 7 hours.The adduct obtained was slightly yellowish in color but clear, and had aviscosity of n=1125 mPas.

[0097] 492.1 parts of the adduct were transferred to a pressure vesseland admixed with 3.0 parts of potassium hydroxide solution (40% strengthby weight), with stirring. The reaction mixture was heated to 150° C.and the water of the potassium hydroxide solution was distilled off overthe course of about 30 minutes with a slight vacuum. Oxethylation wasthen carried out with stirring and introduction of 532.0 parts ofethylene oxide at from 150 to 160° C. over the course of 70 minutes,during which a pressure of about 4 to 6 bar was maintained. After all ofthe ethylene oxide had been injected, stirring was continued at 120° C.internal temperature for 30 minutes more. The oxethylate obtained waspresent at room temperature in the form of a slightly yellowish, cloudyviscous mass with a viscosity of η=27375 mPas.

PREPARATION EXAMPLE 2

[0098] A stirred vessel was charged with 205.9 parts of an amine of theformula (4) with R⁶, R⁷=hydrogen, R⁵=alkyl radical of coconut fattyalcohol, p=0, and q=5, 7.7 parts of oleylamine with a composition of 1%C₁₂, 3% C₁₄, 18% C₁₆, 76% C₁₈, 1% C₂₀, and an iodine number of from 75to 85, and with 0.13 part of phenol under an inert gas atmosphere. Thismixture was heated to an internal temperature of 100° C. and, at thistemperature, 64.8 parts of a finely powdered polyepoxide of theidealized structure in formula (2) with R¹=2-methyl, R², R³,R⁴=hydrogen, n=5, epoxy equivalent weight 225 [g/eq], were added overthe course of 5 minutes. The mixture was heated to an internaltemperature of 120° C., held at this temperature for 4 hours, thenheated to 150° C., and the reaction mixture was stirred at thistemperature for a further 2 hours. The adduct obtained was slightlyyellowish in color but clear, and had a viscosity of η=5328 mPas.

[0099] 224.8 parts of the adduct were transferred to a pressure vesseland admixed with 1.5 parts of potassium hydroxide solution (40% strengthby weight), with stirring. The reaction mixture was heated to 150° C.and the water of the potassium hydroxide solution was distilled off overthe course of about 30 minutes with a slight vacuum. Oxethylation wasthen carried out with stirring and introduction of 295.0 parts ofethylene oxide at from 150 to 160° C. over the course of 40 minutes,during which a pressure of about 4 to 5.5 bar was maintained. After allof the ethylene oxide had been injected, stirring was continued at 120°C. internal temperature for 30 minutes more. The oxethylate obtained waspresent at room temperature in the form of a slightly yellowish, cloudyviscous mass with a viscosity of η=53960 mPas.

PREPARATION EXAMPLE 3

[0100] A stirred vessel was charged with 210.5 parts of an amine of theformula (4) with R⁶, R⁷=hydrogen, R⁵=alkyl radical of coconut fattyalcohol, p=0, and q=5,14.7 parts of di-tallow fatty amine with acomposition of 3% C₁₄, 29% C₁₆, 63% C₁₈, ≦3% C₂₀, and an iodine numberof from 45 to 55, and with 0.13 part of phenol under an inert gasatmosphere. This mixture was heated to an internal temperature of 100°C. and, at this temperature, 66.2 parts of a finely powdered polyepoxideof the idealized structure in formula (2) with R¹=2-methyl, R², R³,R⁴=hydrogen, n=5, epoxy equivalent weight 225 [g/eq], were added overthe course of 5 minutes. The mixture was heated over 45 minutes to aninternal temperature of 150° C. and the reaction mixture was stirred atthis temperature for 7 hours. The adduct obtained was slightly yellowishin color but clear, and had a viscosity of η=2800 mPas.

[0101] 248.7 parts of the adduct were transferred to a pressure vesseland admixed with 1.5 parts of potassium hydroxide solution (40% strengthby weight), with stirring. The reaction mixture was heated to 150° C.and the water of the potassium hydroxide solution was distilled off overthe course of about 30 minutes with a slight vacuum. Oxethylation wasthen carried out with stirring and introduction of 315.0 parts ofethylene oxide at from 150 to 160° C. over the course of 40 minutes,during which a pressure of about 4 to 5.5 bar was maintained. After allof the ethylene oxide had been injected, stirring was continued at 120°C. internal temperature for 30 minutes more. The oxethylate obtained waspresent at room temperature in the form of a slightly yellowish, cloudyviscous mass with a viscosity of η=32170 mPas.

PREPARATION EXAMPLE 4

[0102] A stirred vessel was charged with 160.1 parts of an amine of theformula (4) with R⁶, R⁷=hydrogen, R⁵=alkyl radical of coconut fattyalcohol, p=0, and q=5, 43.2 parts of di-tallow fatty amine with acomposition of 3% C₁₄, 29% C₁₆, 63% C₁₈, ≦3% C₂₀, and an iodine numberof from 45 to 55, and with 0.3 part of phenol under an inert gasatmosphere. This mixture was heated to an internal temperature of 100°C. and, at this temperature, 64.8 parts of a finely powdered polyepoxideof the idealized structure in formula (2) with R¹=2-methyl, R², R³,R⁴=hydrogen, n=5, epoxy equivalent weight 225 [g/eq], were added overthe course of 5 minutes. The mixture was heated for over 45 minutes toan internal temperature of 150° C. and the reaction mixture was stirredat this temperature for 7 hours. The adduct obtained was slightlyyellowish in color but clear, and had a viscosity of η=3742 mPas.

[0103] 209.9 parts of the adduct were transferred to a pressure vesseland admixed with 1.0 part of potassium hydroxide solution (40% strengthby weight), with stirring. The reaction mixture was heated to 150° C.and the water of the potassium hydroxide solution was distilled off overthe course of about 30 minutes with a slight vacuum. Oxethylation wasthen carried out with stirring and introduction of 285.0 parts ofethylene oxide at from 150 to 160° C. over the course of 40 minutes,during which a pressure of about 4 to 5.5 bar was maintained. After allof the ethylene oxide had been injected, stirring was continued at 120°C. internal temperature for 30 minutes more. The oxethylate obtained waspresent at room temperature in the form of a slightly yellowish, cloudyviscous mass with a viscosity of η=46610 mPas.

PREPARATION EXAMPLE 5

[0104] A stirred vessel was charged with 288.0 parts of di-tallow fattyamine with a composition of 3% C₁₄, 29% C₁₆, 63% C₁₈, ≦3% C₂₀, iodinenumber 45 to 55 and with 0.26 part of phenol under an inert gasatmosphere. This mixture was heated to an internal temperature of 100°C. and, at this temperature, 129.6 parts of a finely powderedpolyepoxide of the idealized structure in formula (2) with R¹=2-methyl,R², R³, R⁴=hydrogen, n=5, epoxy equivalent weight 225 [g/eq] , wereadded over the course of 5 minutes. The mixture was heated over thecourse of 45 minutes to an internal temperature of 150° C. and thereaction mixture was stirred at this temperature for 7 hours. Theresulting adduct obtained was a clear viscous mass which was slightlybrownish yellow in color.

[0105] 388.9 parts of the adduct were transferred to a pressure vesseland admixed with 3.0 parts of potassium hydroxide solution (40% strengthby weight), with stirring. The reaction mixture is heated to 150° C. andthe water of the potassium hydroxide solution was distilled off over thecourse of about 30 minutes with a slight vacuum. Oxethylation was thencarried out with stirring and introduction of 937.0 parts of ethyleneoxide at from 150 to 160° C. over the course of 95 minutes, during whicha pressure of about 4 to 5.5 bar was maintained. After all of theethylene oxide had been injected, stirring was continued at 120° C.internal temperature for 30 minutes more. The oxethylate obtained waspresent at room temperature in the form of a slightly yellowish-palebrown, cloudy waxlike mass.

PREPARATION EXAMPLE 6

[0106] A stirred vessel was charged with 290.9 parts of distearylaminewith a composition of 3% C₁₄, 29% C₁₆, 63% C₁₈, ≦3% C₂₀, iodine number≦5 and with 0.26 part of phenol under an inert gas atmosphere. Thismixture was heated to an internal temperature of 100° C. and, at thistemperature, 129.6 parts of a finely powdered polyepoxide of theidealized structure in formula (2) with R¹=2-methyl, R², R³,R⁴=hydrogen, n=5, epoxy equivalent weight 225 [g/eq] , were added overthe course of 5 minutes. The mixture was heated over the course of 45minutes to an internal temperature of 150° C. and the reaction mixturewas stirred at this temperature for 7 hours. The resulting adductobtained was a clear viscous mass which was slightly yellowish in color.

[0107] 396.8 parts of the adduct were transferred to a pressure vesseland admixed with 3.0 parts of potassium hydroxide solution (40% strengthby weight), with stirring. The reaction mixture was heated to 150° C.and the water of the potassium hydroxide solution was distilled off overthe course of about 30 minutes with a slight vacuum. Oxethylation wasthen carried out with stirring and introduction of 950.0 parts ofethylene oxide at from 150 to 160° C. over the course of 120 minutes,during which a pressure of about 4 to 5.5 bar was maintained. After allof the ethylene oxide had been injected, stirring was continued at 120°C. internal temperature for 40 minutes more. The oxethylate obtained waspresent at room temperature in the form of a slightly yellowish-palebrown, cloudy waxlike mass.

PREPARATION EXAMPLE 7

[0108] A stirred vessel was charged with 205.9 parts of an amine of theformula (4) with R⁶, R⁷=hydrogen, R⁵=alkyl radical of coconut fattyalcohol, p=0, and q=5, 1.9 parts of pyrrole and with 0.13 part of phenolunder an inert gas atmosphere. This mixture was heated to an internaltemperature of 100° C. and, at this temperature, 64.8 parts of a finelypowdered polyepoxide of the idealized structure in formula (2) withR¹=2-methyl, R², R³, R⁴=hydrogen, n=5, epoxy equivalent weight 225[g/eq], were added over the course of 5 minutes. The mixture was heatedover 45 minutes to an internal temperature of 150° C. and the reactionmixture was stirred at this temperature for 7 hours. 216.5 parts of theadduct were transferred to a pressure vessel and admixed with 1.0 partof potassium hydroxide solution (40% strength by weight), with stirring.The reaction mixture was heated to 150° C. and the water of thepotassium hydroxide solution was distilled off over the course of about30 minutes with a slight vacuum. Oxethylation was then carried out withstirring and introduction of 285.0 parts of ethylene oxide at from 150to 160° C. over the course of 95 minutes, during which a pressure ofabout 4 to 5.5 bar was maintained. After all of the ethylene oxide hadbeen injected, stirring was continued at 120° C. internal temperaturefor 30 minutes more. The oxethylate obtained was present at roomtemperature in the form of a slightly yellowish brown, cloudy waxlikemass.

PREPARATION EXAMPLE 8

[0109] A stirred vessel was charged with 205.9 parts of an amine of theformula (4) with R⁶, R⁷=hydrogen, R⁵=alkyl radical of coconut fattyalcohol, p=0, and q=5, and with 0.13 part of phenol under an inert gasatmosphere. This mixture was heated to an internal temperature of 100°C. and, at this temperature, 64.8 parts of a finely powdered polyepoxideof the idealized structure in formula (2) with R¹=2-methyl, R², R³,R⁴=hydrogen, n=5, epoxy equivalent weight 225 [g/eq], were added overthe course of 5 minutes. The mixture was heated over 45 minutes to aninternal temperature of 150° C. and the reaction mixture was stirred atthis temperature for 5 hours. Thereafter, still at this temperature, 3.6parts of 1,3-aminopropylamidazole are added in one portion and thereaction mixture is stirred at this temperature for 2 hours more. Theadduct obtained was red-brownish in color but clear, and had a viscosityof η=11230 mPas.

[0110] 218.8 parts of the adduct were transferred to a pressure vesseland admixed with 1.0 part of potassium hydroxide solution (40% strengthby weight), with stirring. The reaction mixture was heated to 150° C.and the water of the potassium hydroxide solution was distilled off overthe course of about 30 minutes with a slight vacuum. Oxethylation wasthen carried out with stirring and introduction of 285.0 parts ofethylene oxide at from 150 to 160° C. over the course of 40 minutes,during which a pressure of about 4 to 5.5 bar was maintained. After allof the ethylene oxide had been injected, stirring was continued at 120°C. internal temperature for 30 minutes more. The resulting oxethylateobtained took the form at room temperature of a deep brown, cloudyviscous mass with a viscosity of viscosity of η=35930 mPas.

PREPARATION EXAMPLE 9

[0111] A stirred vessel was charged with 116.0 parts of a polyepoxide ofthe idealized structure in formula (2) with R¹, R², R³, R⁴=hydrogen,n=1.2, epoxy equivalent weight 175 [g/eq] (Araldite EPN 1179) and 0.26part of phenol under an inert gas atmosphere. This mixture was heated toan internal temperature of 100° C. and at this temperature 524.2 partsof an amine of the formula (4) with R⁶, R⁷=hydrogen, R⁵=alkyl radical ofcoconut fatty alcohol, p=0, and q=5 were added over the course of 15minutes. Over the course of 45 minutes the mixture was heated to aninternal temperature of 160° C. and the reaction mixture was stirred atthis temperature for 8 hours. The resulting adduct was slightlyyellowish in color but clear, and had a viscosity of η=456 mPas.

[0112] 493.5 parts of the adduct were transferred to a pressure vesseland 3.0 parts of the potassium hydroxide solution (40% strength byweight) were added with stirring. The reaction mixture was heated to150° C. and the water of the potassium hydroxide solution was distilledoff over the course of about 30 minutes with a gentle vacuum. Thenoxethylation was carried out with stirring and introduction of 560.3parts of ethylene oxide at 150 to 160° C. over the course of 60 minutes,during which a pressure of about 4 to 6 bar was maintained. After all ofthe ethylene oxide had been injected, stirring was continued at aninternal temperature of 120° C. for 30 minutes more. The oxethylateobtained took the form at room temperature of a pale-yellowish, cloudy,viscous mass.

PREPARATION EXAMPLE 10

[0113] A stirred vessel was charged with 491.6 parts of tallow fattyamine with a composition of 3 % C₁₄, 29 % C₁₆, 63 % C₁₈, ≦3 % C₂₀,iodine number from 40 to 50, amine number 208 to 220 under an inert gasatmosphere and this initial charge was heated to an internal temperatureof 140° C. At this temperature 328.5 parts of a polyepoxide of theidealized structure in formula (2) with R¹, R², R³, R⁴=hydrogen, n=1.5,epoxy equivalent weight 175 [g/eq] (®Araldite PY 307-1) are addedcontinuously over the course of 6 hours. Thereafter the batch wasstirred at this temperature for 2 hours more. The adduct obtained was apale waxlike mass at room temperature.

[0114] 224.8 parts of the adduct were transferred to a pressure vesseland 3.0 parts of potassium hydroxide solution (40% strength by weight)were added with stirring. The reaction mixture was heated to 150° C. andthe water of the potassium hydroxide solution was distilled off over thecourse of about 30 minutes with a gentle vacuum. Then oxethylation wascarried out with stirring and introduction of 905.0 parts of ethyleneoxide at 150 to 160° C. over the course of 95 minutes, during which apressure of about 4 to 5.5 bar was maintained. After all of the ethyleneoxide had been injected, stirring was continued at an internaltemperature of 120° C. for 30 minutes more. The oxethylate obtained tookthe form at room temperature of a pale yellowish-light brown, solid,waxlike mass.

[0115] Preparation of Adduct Oxalkylate Sulfosuccinates

PREPARATION EXAMPLE 11

[0116] In a stirred vessel, 375.0 parts of oxethylate from PreparationExample 1 were mixed with 17.35 parts of maleic anhydride at roomtemperature under an inert gas atmosphere and slight superatmosphericpressure, in order to prevent sublimation of the maleic anhydride. Thereaction mixture was then heated first at an internal temperature of 70°C. for 1 hour, then stirred at an internal temperature of 85 to 90° C.for a further 2 hours. During this time the viscosity of the reactionmixture rose markedly and took on a gelatinous consistency. Subsequentlya solution of 22.30 parts of sodium sulfite in 1658.0 parts ofdemineralized water was run in over the course of 1 hour at an internaltemperature of 70° C., followed by stirring at this temperature for 3hours until the batch had become soluble in water to give a clearsolution. The pH of the solution was then adjusted to 7.0 using NaOHsolution (50% strength). At room temperature the product takes the formof a clear solution, slightly yellowish in color, with a viscosity ofη=175 mPas and has a solids concentration of 20% by weight.

PREPARATION EXAMPLE 12

[0117] In a stirred vessel, 100.0 parts of oxethylate from PreparationExample 5 were mixed with 4.7 parts of maleic anhydride at roomtemperature under an inert gas atmosphere and slight superatmosphericpressure, in order to prevent sublimation of the maleic anhydride. Thereaction mixture was then heated at an internal temperature of 75° C.for 4 hours. During this time the viscosity of the reaction mixture rosemarkedly. Subsequently a solution of 6.05 parts of sodium sulfite and443.0 parts of demineralized water was run in over the course of 5minutes at an internal temperature of 70° C., followed by stirring atthis temperature for 2 hours until the batch became soluble in water togive a clear solution. The pH of the solution was then adjusted to 7.0using NaOH solution (50% strength). At room temperature the producttakes the form of a clear solution, slightly yellowish in color, with aviscosity of η=53 mPas and has a solids concentration of 20% by weight.

USE EXAMPLES

[0118] General Remarks

[0119] To produce the pigment preparations first of all theconstituents, without the respective pigment, were homogenized in theempty grinding part of a laboratory bead mill in accordance with theformulations set out in the examples below. Using a sawtooth disk thepulverulent pigment was then incorporated and the amount of water chosenwas such as to give a homogeneous, readily stirrable dough. Thereafter,grinding media were added and grinding was commenced. After the firstmixing of the grinding medium at the beginning of the grinding operationthe optimum grinding viscosity was set accordingly by adding water.After the grinding operation the grinding media were separated off, forexample, by filtration and/or centrifugation.

[0120] For suitability testing the pigment preparations were stirred ata concentration of to 1 to 5% into different, commercially availablestandard white emulsion paints, applied as a thin film and thenevaluated coloristically (white reduction).

[0121] It is also possible to incorporate the pigment preparation into atest varnish in order to assess the varnish compatibility.

[0122] As well as the incorporation of the pigment preparation into thewhite emulsion paint or test varnish, by stirring with a spatula, ananalogous sample was prepared by stirring it in using a dissolver disk.Both samples were compared with one another for color strength. In thisevaluation, values close to 100% indicate excellent dispersing and ahigh level of compatibility of the pigment preparation with emulsionpaints and varnish.

[0123] To test the dispersibility and flocculation stability in theapplication medium, a portion of the film, following brief initialdrying, was rubbed repeatedly with a brush or with a finger undermoderate pressure. If the pigment preparation cannot be satisfactorilydispersed in the test medium or if flocculation occurs when thepreparation is introduced into the test medium, then flocculatedand/agglomerated pigment particles are at least partly deflocculated anddeagglomerated by the shearing force exerted on the film by rubbing. Inthat case the area thus treated has either a higher color strengthand/or an irregular or unequal shade as compared with the unrubbed area.This test method, referred to as the rubout test, is suitable as asimple but usually very sensitive method of assessing the quality of thepigment preparation in terms of dispersibility and flocculationstability. A test of this kind is widely described in the literature,e.g., in FARBE & LACKE 100, Volume 6/2000, 51-61.

[0124] To test the storage stability, a sample of the pigmentpreparation is stored hot at 50-60° C. in a closed vessel for 4 to 5weeks. The viscosity and coloristic data of the samples are measuredboth before and after this storage. If the preparation remains fluid orif there is little change in the rheology and coloristics, this islikewise an indication of the higher quality of dispersing which can beachieved with the dispersing auxiliaries of the invention.

USE EXAMPLE 1

[0125] 29 parts of C.I. Pigment Violet 23, 12 parts of dispersingauxiliary from Preparation Example 1, 20 parts of glycol, 0.2 part ofpreservative and 38.8 parts of demineralized water are ground at 35 to38° C. using a DCP Super Flow bead mill (from Drais) with 110 parts ofzirconium oxide beads (d=0.6 to 0.9 mm) in 2 passes (in each case aresidence time of 9 minutes in the grinding zone). The pigmentpreparation has a high color strength with a very clean shade, and isfound to be highly fluid (η=499 mPas) and storage-stable, i.e., thesample remains fluid despite hot storage at 50° C. for 5 weeks (η=1159mPas). The manual-stirrer dispersing of 100% in the white reduction (1%concentration) is evidence of the excellent dispersing and high emulsionpaint compatibility of the pigment preparation. The pigment preparationpossesses excellent stability to dryout. In the white reductions (1%concentration) there are also no rubout effects at all, i.e., the rubbedarea of the colorations is identical in color strength with noirregularities in shade.

USE EXAMPLE 2

[0126] Using in Use Example 1 the dispersing auxiliary from PreparationExample 2 gives a pigment preparation again having good Theologicalproperties (viscosity prior to hot storage η=507 mPas, good fluidityafter hot storage for 5 weeks) and having comparable coloristicproperties in the white reductions (1% concentration).

USE EXAMPLE 3

[0127] Using in Use Example 1 the dispersing auxiliary from PreparationExample 3 gives a pigment preparation again having good Theologicalproperties (viscosity prior to hot storage η=441 mPas, good fluidityafter hot storage for 5 weeks at 50° C.) and having comparablecoloristic properties in the white reductions (1% concentration).

USE EXAMPLE 4

[0128] Using in Use Example 1 the dispersing auxiliary from PreparationExample 4 gives a pigment preparation again having good Theologicalproperties (viscosity prior to hot storage η=384 mPas, good fluidityafter hot storage for 5 weeks at 50° C.) and having comparablecoloristic properties in the white reductions (1% concentration).

USE EXAMPLE 5

[0129] Using in Use Example 1 the dispersing auxiliary from PreparationExample 5 gives a pigment preparation with somewhat higher viscosity(viscosity prior to hot storage η=2448 mPas) and very good coloristicproperties in the white reductions (1% concentration).

USE EXAMPLE 6

[0130] Using in Use Example 1 the dispersing auxiliary from PreparationExample 6 gives a pigment preparation having good rheological properties(viscosity prior to hot storage η=1448 mPas, adequate fluidity after hotstorage for 5 weeks at 50° C.) and having comparable coloristicproperties in the white reductions (1% concentration).

USE EXAMPLE 7

[0131] Using in Use Example 1 the dispersing auxiliary from PreparationExample 7 gives a pigment preparation having similarly good Theologicalproperties (viscosity prior to hot storage η=1057 mPas, adequatefluidity after hot storage for 5 weeks at 50° C.) and having comparablecoloristic properties in the white reductions (1% concentration).

USE EXAMPLE 8

[0132] Using in Use Example 1 the dispersing auxiliary from PreparationExample 8 gives a pigment preparation again with good rheologicalproperties (viscosity prior to hot storage η=879 mPas, good fluidityafter hot storage for 5 weeks at 50° C.) and having comparablecoloristic properties in the white reductions (1% concentration).

USE EXAMPLE 9

[0133] 40 parts of C.I. Pigment Red 146,14 parts of dispersing auxiliaryfrom Preparation Example 1, 5 parts of urea, 13 parts of glycol, 0.2part of preservative and 27.8 parts of demineralized water were groundat 35 to 40° C. using a laboratory bead mill (from Drais) with 275 partsof glass beads (d=1 mm) for 60 minutes. The pigment preparation had ahigh color strength with a very clean shade, and is found to be highlyfluid (η=268 mPas) and storage-stable, i.e., the sample remainedrelatively fluid despite hot storage at 50° C. for 5 weeks (η=1964mPas). The manual-stirrer dispersing of 101% in the white reduction (1%concentration) is evidence of the excellent dispersing and high emulsionpaint compatibility of the pigment preparation. The pigment preparationpossesses excellent stability to dryout. In the white reductions (1%concentration) there are also no rubout effects at all, i.e., the rubbedarea of the colorations is identical in color strength with noirregularities in shade.

USE EXAMPLE 10

[0134] 70 parts of C.I. Pigment Green 50, 13 parts of dispersingauxiliary from Preparation Example 1, 0.4 part of oleylamine, 14 partsof glycol, 0.2 part of preservative and 2.4 parts of demineralized waterwere ground at 35 to 40° C. using a laboratory bead mill (from Drais)with 275 parts of glass beads (d=1 mm) for 60 minutes. The pigmentpreparation had a high color strength with a very clean shade, and isfound to be highly fluid (η=2643 mPas) for an inorganic pigmentpreparation and storage-stable, i.e., the sample remained relativelyfluid despite hot storage at 50° C. for 5 weeks (η=3412 mPas). Themanual-stirrer dispersing of 100% in the white reduction (5%concentration) is evidence of the excellent dispersing and high emulsionpaint compatibility of the pigment preparation. The pigment preparationpossesses excellent stability to dryout. In the white reductions (5%concentration) there are also no rubout effects at all, i.e., the rubbedarea of the colorations is identical in color strength with noirregularities in shade.

USE EXAMPLE 11

[0135] 42 parts of C.I. Pigment Black 7, 6.0 parts of dispersingauxiliary from Preparation Example 1, 20 parts of glycol, 0.2 part ofpreservative and 31.8 parts of demineralized water were ground at 35 to40° C. using a laboratory bead mill (from Drais) with 275 parts of glassbeads (d=1 mm) for 40 minutes. The pigment preparation had a high colorstrength with a very clean shade, and is found to be highly fluid (η=582mPas) for a carbon black preparation and storage-stable, i.e., thesample remained relatively fluid despite hot storage at 50° C. for 5weeks (η=1063 mPas). The manual-stirrer dispersing of 100% in the whitereduction (1% concentration) is evidence of the excellent dispersing andhigh emulsion paint compatibility of the pigment preparation. Thepigment preparation possesses excellent stability to dryout. In thewhite reductions (1% concentration) there are also no rubout effects atall, i.e., the rubbed area of the colorations is identical in colorstrength with no irregularities in shade.

USE EXAMPLE 12

[0136] 42 parts of C.I. Pigment Black 7, 6.5 parts of dispersingauxiliary from Preparation Example 9, 20 parts of glycol, 0.2 part ofpreservative and 31.3 parts of demineralized water were ground at 35 to40° C. using a laboratory bead mill (from Drais) with 275 parts of glassbeads (d=1 mm) for 20 minutes. The pigment preparation had a high colorstrength with a very clean shade, and is found to be highly fluid (η=350mPas) for a carbon black preparation and storage-stable, i.e., thesample remained relatively fluid despite hot storage at 50° C. for 5weeks (η=440 mPas). The manual-stirrer dispersing of 100% in the whitereduction (1% concentration) is evidence of the excellent dispersing andhigh emulsion paint compatibility of the pigment preparation. Thepigment preparation possesses excellent stability to dryout. In thewhite reductions (1% concentration) there are also no rubout effects atall, i.e., the rubbed area of the colorations is identical in colorstrength with no irregularities in shade.

USE EXAMPLE 13

[0137] 35 parts of C.I. Pigment Yellow 83, 8 parts of dispersingauxiliary from Preparation Example 10, 15 parts of glycol, 0.2 part ofpreservative and 41.8 parts of demineralized water are ground at 35 to38° C. using a DCP Super Flow bead mill (from Drais) with 110 parts ofzirconium oxide beads (d=0.6 to 0.9 mm) in 2 passes (in each case aresidence time of 9 minutes in the grinding zone). The pigmentpreparation has a high color strength with a very clean shade, and isfound to be highly fluid (η=91 mPas) and storage-stable, i.e., thesample remains highly fluid despite hot storage at 50° C. for 5 weeks(η=78 mPas). The manual-stirrer dispersing of 100% in the white reaction(1% concentration) is evidence of the excellent dispersing and highemulsion paint compatibility of the pigment preparation. The pigmentpreparation possesses excellent stability to dryout. In the whitereductions (1% concentration) there are also no rubout effects at all,i.e., the rubbed area of the colorations is identical in color strengthwith no irregularities in shade.

[0138] The pigment preparation was outstandingly suitable for producingprinting inks for inkjet printing. On a variety of papers prints withoutstanding color brightness were produced.

USE EXAMPLE 14

[0139] 40 parts of C.I. Pigment Yellow 97, 14 parts of dispersingauxiliary from Preparation Example 1, 15 parts of glycol, 0.2 part ofpreservative and 30.8 parts of demineralized water were ground at 35 to40° C. using a laboratory bead mill (from Drais) with 275 parts of glassbeads (d=1 mm) for 60 minutes. The pigment preparation had a high colorstrength with a very clean shade, and is found to be outstandingly fluid(η=510 mPas) and storage-stable, i.e., the sample remained relativelyfluid despite hot storage at 50° C. for 5 weeks (η=549 mPas). Themanual-stirrer dispersing of 100% in the white reduction (1%concentration) is evidence of the excellent dispersing and high emulsionpaint compatibility of the pigment preparation. The pigment preparationpossessed excellent stability to dryout. In the white reductions (1%concentration) there were also no rubout effects at all, i.e., therubbed area of the colorations was identical in color strength with noirregularities in shade.

USE EXAMPLE 15

[0140] 33 parts of C.I. Pigment Yellow 154, 7.5 parts of dispersingauxiliary from Preparation Example 1, 17 parts of glycol, 0.2 part ofpreservative and 42.3 parts of demineralized water were ground at 35 to40° C. using a laboratory bead mill (from Drais) with 275 parts of glassbeads (d=1 mm) for 60 minutes. The pigment preparation had a high colorstrength with a very clean shade, and is found to be highly fluid (η=686mPas) and storage-stable, i.e., the sample remained relatively fluiddespite hot storage at 50° C. for 5 weeks (η=1 257 mPas). Themanual-stirrer dispersing of 101% in the white reduction (1%concentration) is evidence of the excellent dispersing and high emulsionpaint compatibility of the pigment preparation. The pigment preparationpossessed excellent stability to dryout. In the white reductions (1%concentration) there were also no rubout effects at all, i.e., therubbed area of the colorations was identical in color strength with noirregularities in shade.

USE EXAMPLE 16

[0141] 48 parts of C.I. Pigment Red 112, 32.25 parts of dispersingauxiliary from Preparation Example 11, 9.5 parts of glycol, 0.2 part ofpreservative and 10.05 parts of demineralized water were ground at 35°C. using a laboratory bead mill (from Drais) with 275 parts of glassbeads (d=1 mm) for 80 minutes. The pigment preparation had a high colorstrength with a very clean shade and is found to be highly stable onstorage, i.e., the sample remained fluid despite hot storage at 50° C.for four weeks. The pigment preparation was notable for a very lowdrying and dryup tendency. In the white reductions (1% concentration),moreover, there were no rubout effects at all, i.e., the rubbed area ofthe colorations was identical in color strength, with no irregularitiesin shade. Owing to the anionic nature of the pigment preparation it isoutstandingly suitable for coloring paper pulp using polycationicflocculation reagents, an application in which high color strength andbright colorations are achievable.

USE EXAMPLE 17

[0142] Using in Use Example 16 the dispersing auxiliary from PreparationExample 12 gives a pigment preparation having similarly good properties.

USE EXAMPLE 18

[0143] 40 parts of C.I. Pigment Yellow 74, 7.0 parts of dispersingauxiliary from Preparation Example 1, 0.6 part of preservative and 52.4parts of demineralized water were ground at 35° C. using a laboratorybead mill (from Drais) with 275 parts of glass beads (d=1 mm) for 60minutes. The pigment preparation had a high color strength with a veryclean shade, and is found to be outstandingly fluid (η=64 mPas) andstorage-stable, i.e., the sample remained fluid despite hot storage at50° C. for 5 weeks (η=673 mPas). The manual-stirrer dispersing of 100%in the white reduction (1% concentration) is evidence of the excellentdispersing and high emulsion paint compatibility of the pigmentpreparation.

[0144] The pigment preparation was notable for a very low drying anddryup tendency. In the white reductions (1% concentration) there arealso no rubout effects at all, i.e., the rubbed area of the colorationswas identical in color strength with no irregularities in shade.

USE EXAMPLE 19

[0145] 30 parts of C.I. Pigment Yellow 154; 9.0 parts of dispersingauxiliary from Preparation Example 1, 7.5 parts of polyethylene glycol(molecular weight 500), 0.6 part of preservative and 52.9 parts ofdemineralized water were ground at 35° C. to 40° C. using a laboratorybead mill (from Drais) with 275 parts of glass beads (d=1 mm) for 60minutes. The pigment preparation had a high color strength with a veryclean shade, and is found to be outstandingly fluid (η=246 mPas) andstorage-stable, i.e., the sample remained fluid despite hot storage at50° C. for 5 weeks (η=855 mPas). The manual-stirrer dispersing of 100%in the white reduction (1% concentration) is evidence of the excellentdispersing and high emulsion paint compatibility of the pigmentpreparation. The pigment preparation was notable in particular for avery low drying and dryup tendency. In the white reductions (1%concentration) there are also no rubout effects at all, i.e., the rubbedarea of the colorations was identical in color strength with noirregularities in shade.

1) An addition compound of the formula (1)

in which n is a number from 1 to 10; R¹, R² are identical or differentand are each a hydrogen atom or a saturated or unsaturated aliphaticradical having 1 to 4 carbon atoms; R³, R⁴ are identical or differentand are each a hydrogen atom or alkyl having 1 to 3 carbon atoms, andthe bridge member

is in each case positioned ortho or meta in relation to the phenolicoxygen atom; z is a group —CH₂—CH₂—, —CH₂—CH(CH₃)—, —CH(CH₃)—CH₂— or acombination thereof, s is a number between 1 and 200, B is hydrogen,—CO—CH═CH—COOM, —COCH (SO₃M)CH₂COOM, —CO—CH₂—CH(SO₃M)-COOM, —SO₃M, —SO₂Mand/or —PO₃MM, M being a cation; and Y is a radical of an amine offormula (4)

in which R⁵ is a saturated or singly or multiply unsaturated aliphaticradical having 6 to 30 carbon atoms, A is phenylene or naphthylene, p iszero or 1, R⁶, R⁷ are each hydrogen or a methyl radical, but are notsimultaneously a methyl radical, and q is a number from 0 to 40; and/orY is a radical of an amine of the formula (5)

in which r is a number from 0 to 2, R⁸ is a saturated or singly ormultiply unsaturated aliphatic radical having 8 to 24 carbon atoms, andR⁹ is an alkylene group having 2 to 6 carbon atoms, and/or Y is aradical of the amines of the formulae (6), (7), (8) and/or (9)

in which t is 0 or 1, R¹⁰ is an alkylene group having 1 to 10 carbonatoms, R¹¹ is an alkylene group having from 2 to 6 carbon atoms, R¹² isa hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R¹³ is asaturated or a singly or multiply unsaturated, mononuclear orpolynuclear heterocyclic or carbocyclic ring system having 3 to 18carbon atoms which if desired also contains in the ring 1, 2 or 3further heteroatoms from the group N, S and O, it being possible for thering system to be substituted by one or more of the radicals R¹⁷,halogen atoms, —OR¹⁷, —NR¹⁷R¹⁸, —COOR¹⁷, —CONR¹⁷R¹⁸, —NR¹⁷—COR¹⁸, —NO₂,—CN or CF₃, R¹⁷ and R¹⁸ independently of one another being hydrogen oran alkyl radical having 1 to 10 carbon atoms, R¹⁴, R¹⁵ are identical ordifferent and are each a saturated or singly or multiply unsaturatedaliphatic radical having 1 to 24 carbon atoms; and R¹⁶ together with thenitrogen atom of the formula (9) forms a 5- to 7-membered heterocyclicring system which if desired-also contains in the ring 1, 2 or 3 furtherheteroatoms from the group N, S and O, it being possible for the ringsystem to be substituted by one or more of the radicals R¹⁷, halogenatoms, —OR¹⁷, —NR¹⁷R¹⁸, —COOR¹⁷, —CONR¹⁷R¹⁸, —NR¹⁷—COR¹⁸, —NO₂, —CN orCF₃. 2) An addition compound as claimed in claim 1, wherein n is anumber from 1.2 to
 6. 3) An addition compound as claimed in claim 1 or2, wherein s is a number from 5 to 100, in particular from 10 to
 40. 4)An addition compound as claimed in one or more of claims 1 to 3, whereinR⁵ is C₆-C₁₈-alkyl or C₆-C₁₈-alkenyl. 5) An addition compound as claimedin one or more of claims 1 to 4, wherein R⁹ is propylene or butylene. 6)An addition compound as claimed in one or more of claims 1 to 5, whereinR¹¹ is ethylene or propylene. 7) An addition compound as claimed in oneor more of claims 1 to 5, wherein the compound of the formula (9) ispyrazole, triazole, piperidine, oxazolidine, imidazole, pyrrole,pyrrolidine, carbazole, dihydropyrrole, dihydropyrazole, oxazolidone,morpholine, dihydropyridine or azepine. 8) A process for preparing anaddition compound as claimed in one or more of claims 1 to 7, byreacting an epoxy compound of the formula (2)

in which X has the definition 2,3-epoxypropyl, with one or more aminesof the formulae (4) to (9), oxalkylating the product, and subjecting theresulting oxalkylate, where appropriate, to monoesterification withmaleic anhydride and, where appropriate, to sulfation. 9) Use of anaddition compound as claimed in one or more of claims 1 to 7 fordispersing solids, especially dyes or pigments. 10) The use as claimedin claim 9 for dispersing in aqueous liquids. 11) A pigment preparationcontaining a) from 1 to 80% by weight of one or more pigments; b) from 1to 50% by weight of at least one addition compound as claimed in one ormore of claims 1 to 8; c) from 0 to 50% by weight of customaryadditives; and d) from 10 to 80% by weight of water, based in each caseon the overall weight (100% by weight) of the pigment preparation. 12) Apigment preparation as claimed in claim 11, wherein the pigment is fromthe class of the monoazo pigments, disazo pigments, laked azo pigments,triphenylmethane pigments, thioindigo pigments, thiazineindigo pigments,perylene pigments, perinone pigments, anthanthrone pigments,diketopyrrolopyrrole pigments, dioxazine pigments, quinacridonepigments, phthalocyanine pigments, isoindolinone pigments, isoindolinepigments, benzimidazolone pigments, naphthol pigments and quinophthalonepigments or carbon blacks. 13) A pigment preparation as claimed in claim11, wherein the pigment is in the class of the titanium dioxides, zincsulfides, iron oxides, chromium oxides, ultramarine, nickel or chromiumantimony titanium oxides, cobalt oxides or bismuth vanadates. 14) Aprocess for producing a pigment preparation as claimed in any of claims11 to 13, by adding the compound(s) of the formula (1), and whereappropriate the further additives, during pigment synthesis or duringgrinding, dispersing or finishing of the pigment.